CN113054157A - Double-composite modified spinel lithium manganate positive plate, preparation method thereof and lithium ion battery - Google Patents
Double-composite modified spinel lithium manganate positive plate, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a double-composite modified spinel lithium manganate positive plate which is prepared from 6-9 parts by mass of spinel lithium manganate, 1-4 parts by mass of lithium manganese iron phosphate, an inorganic solid electrolyte, a conductive agent and a binder; the mass of the inorganic solid electrolyte is 0.3-3% of the total mass of the spinel lithium manganate and the lithium iron manganese phosphate. The invention also discloses a preparation method of the double-composite modified spinel lithium manganate positive plate and a lithium ion battery prepared from the double-composite modified spinel lithium manganate positive plate. The double-composite modified spinel lithium manganate positive plate disclosed by the invention is low in cost and easy for large-scale production, and can improve the performance of a lithium manganate battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a double-composite modified spinel lithium manganate positive plate, a preparation method thereof and a lithium ion battery.
Background
The spinel lithium manganate material has the advantages of rich resources, low cost, high voltage, good low-temperature performance and the like, but in the charging and discharging process, trivalent Mn in the material is easy to disproportionate to generate soluble divalent Mn, so that the structure is changed, particularly, hydrofluoric acid decomposed by lithium hexafluorophosphate plays a role in catalysis at high temperature, so that the structure change of lithium manganate is accelerated, and therefore, the high-temperature performance of lithium manganate is poor.
The lithium iron manganese phosphate material has a stable olivine structure, does not change in the structure in the lithium ion de-intercalation process, and has good high-temperature cycle performance. Therefore, by means of doping and cladding, lithium iron manganese phosphate is adopted to modify the spinel lithium manganate material, and the cycle performance of the spinel lithium manganate can be improved.
The Chinese patent with publication number CN104134815A discloses a mixed anode material and application, wherein two substances of lithium manganate and lithium manganese iron phosphate are mixed to serve as an anode active material, the method improves the cycle and safety performance, but the particle size of the lithium manganese iron phosphate is large, the lithium ion deintercalation is influenced, the pole piece compaction is reduced, and the improvement effect is limited. The Chinese patent with publication number CN108987671A discloses a high-safety composite positive pole piece, a preparation method and an application thereof, wherein the composite positive pole piece comprises an energy layer and a hardly oxygen-deprived layer prepared from specific raw materials, so that the composite positive pole piece has high needling resistance safety and extrusion resistance safety. The energy layer comprises an energy anode material; the energy positive electrode material comprises one or more of lithium cobaltate and a modified material thereof, a lithium nickel cobalt manganese oxide ternary material and a modified material thereof, a lithium nickel cobalt aluminate ternary material and a modified material thereof, lithium manganese oxide and a modified material thereof, lithium nickel manganese oxide and a modified material thereof, and a lithium-rich phase material and a modified material thereof. The oxygen loss-resistant layer comprises an oxygen loss-resistant positive electrode material; the oxygen loss-resistant positive electrode material comprises one or more of lithium iron phosphate and a modified material thereof, lithium vanadium phosphate and a modified material thereof, lithium manganese iron phosphate and a modified material thereof, lithium manganese phosphate and a modified material thereof, lithium iron silicate and a modified material thereof, and lithium manganese iron silicate and a modified material thereof. The method mainly emphasizes the improvement of the phosphate system material on the safety performance, and the coating thickness is too thick, so that the transportation of ions and electrons is hindered, and relevant data support is not provided for the cycle performance.
Therefore, a new method for applying lithium iron manganese phosphate and lithium manganate to the positive plate is needed to overcome the technical problems and the cost problems, and obtain the composite positive plate which has excellent performance, low cost and easy large-scale production.
Disclosure of Invention
The invention aims to provide a preparation method of a double-composite modified spinel lithium manganate positive plate and a lithium ion battery.
The invention provides a double-composite modified spinel lithium manganate positive plate which is prepared from 6-9 parts by mass of spinel lithium manganate, 1-4 parts by mass of lithium manganese iron phosphate, an inorganic solid electrolyte, a conductive agent and a binder; the mass of the inorganic solid electrolyte is 0.3-3% of the total mass of the spinel lithium manganate and the lithium iron manganese phosphate.
Preferably, the positive plate comprises 7-8 parts by mass of spinel lithium manganate and 2-3 parts by mass of lithium manganese iron phosphate.
In the invention, the spinel lithium manganate is capacity type lithium manganate D 509 to 18 μm; or the spinel lithium manganate is single crystal lithium manganate D 506 to 12 μm.
In the invention, the molecular formula of the lithium manganese iron phosphate is LiMnxFe1-xPO4Wherein 0 is<x<1. Preferably, the lithium manganese iron phosphate is LiMn0.5Fe0.5PO4、LiMn0.6Fe0.4PO4、LiMn0.7Fe0.3PO4、LiMn0.8Fe0.2PO4、LiMn0.9Fe0.1PO4One kind of (1). Preferably, D of the lithium iron manganese phosphate50Is 1 &3 μm, electron conductivity greater than 10-4S/cm。
In the positive plate material, small-particle lithium manganese iron phosphate and large-particle spinel lithium manganate jointly form an active substance of the positive plate, and the mass ratio of the small-particle lithium manganese iron phosphate to the large-particle spinel lithium manganate is preferably 1: 2-1: 10. On one hand, the submicron lithium manganese iron phosphate has high electronic conductivity, and is filled in gaps among large-particle spinel lithium manganate to construct a good electronic channel, so that the space utilization rate is high, and the compaction density is high; on the other hand, the lithium manganate can be coated on the surface of spinel lithium manganate to reduce side reactions, thereby being beneficial to improving the cycle performance of lithium manganate.
In the invention, the mass of the inorganic solid electrolyte is 0.3-3% of that of active substances (spinel lithium manganate and lithium manganese iron phosphate). If the content of the inorganic solid electrolyte is too low, the effect of constructing a fast channel of lithium ions is not achieved, and if the content is too high, the amount of the active material is reduced. D of the inorganic solid electrolyte50Preferably 50 to 300nm, the smaller the particle size, the easier the connection of the active material, but the smaller the particle size, difficult to disperse, high preparation cost, and the use of mature sand mill for nano-crystallization is easy to reach 50 to 300nm size. The inorganic solid electrolyte may employ an inorganic solid electrolyte commonly used in the art, and is preferably one of Lithium Aluminum Titanium Phosphate (LATP), Lithium Lanthanum Titanate (LLTO), and Lithium Lanthanum Zirconium Oxide (LLZO).
In the invention, the conductive agent can be selected from conductive agents commonly used in the field, and is preferably one or a mixture of more than two of carbon black conductive agents (sp), graphite conductive agents and Carbon Nanotubes (CNTs). The binder can be selected from binders commonly used in the art, preferably polyvinylidene fluoride (PVDF).
The double-composite modified spinel lithium manganate positive plate can be prepared through the steps (i) or (ii):
(i) mixing spinel lithium manganate, lithium manganese phosphate, inorganic solid electrolyte, conductive agent and binder by a dry method, adding N-methylpyrrolidone (NMP), and mixing to form a viscous paste; adding N-methyl pyrrolidone, and stirring at a high rotating speed to obtain a slurry with the viscosity of 10000-30000 mpa.s; coating the slurry on a current collector, drying, and rolling to obtain the double-composite modified spinel lithium manganate positive plate;
(ii) mixing spinel lithium manganate, lithium manganese phosphate, a conductive agent and part of a binder by a dry method, adding N-methyl pyrrolidone, and mixing to form a viscous paste; adding N-methyl pyrrolidone, increasing the rotating speed, stirring, and adjusting the viscosity of the slurry to 10000-30000 mpa.s to obtain slurry A; carrying out sanding nanocrystallization on the inorganic solid electrolyte, the residual binder and N-methyl pyrrolidone to prepare slurry B with the viscosity of 5000-10000 mpa.s; coating the slurry A on a current collector and drying, coating the slurry B on the current collector and drying, and rolling to obtain the double-composite modified spinel lithium manganate positive plate.
In the preparation steps, the solid substances are mixed by a dry method firstly and prepared into a pasty mixture, and the main purpose is to fully disperse the lithium iron manganese phosphate submicron particles and the inorganic solid electrolyte nano particles among the spinel lithium manganese oxide and avoid agglomeration.
In the above preparation steps, the positive plate can be prepared by one of extrusion coating, transfer coating, micro-gravure coating and blade coating.
In the step (ii), the inorganic solid electrolyte is separately prepared into slurry and then coated, so that the nano-scale inorganic solid electrolyte can be better prevented from agglomerating.
In both steps (i) and (ii) above, the solids content of the slurry is preferably 40% to 70%.
In the step (i), the coating density of the slurry is preferably 150 to 300g/m2(ii) a In the step (ii), the coating density of the slurry A is preferably 150-300 g/m2The coating thickness of the slurry B is preferably 1-3 μm.
In the steps (i) and (ii), the compacted density after rolling is preferably 3.1-3.4 g/cm3。
The invention also provides a lithium ion battery which comprises a positive plate, a negative plate, electrolyte and a diaphragm, wherein the positive plate is the double-composite modified spinel lithium manganate positive plate.
Preferably, the electrolyte is an organic electrolyte.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the invention creatively mixes the submicron-grade lithium iron manganese phosphate cathode material, the inorganic solid electrolyte and the spinel lithium manganate for use, and utilizes the characteristics of high electronic conductivity (figure 1), small internal resistance and high ionic conductivity of the nano inorganic solid electrolyte of the submicron-grade lithium iron manganese phosphate to compound with the spinel lithium manganate, thereby reducing the polarization and manganese dissolution of the lithium manganate and improving the cycle performance.
2. According to the invention, the proportion and the particle diameter ratio of the mixed lithium iron manganese phosphate and spinel lithium manganate anode material are controlled, the compounding amount of the inorganic solid electrolyte is controlled, a high-speed ion and electron double-transmission channel is established, and the small particles are combined to fill the gaps among the large particles, so that the compaction density is improved, and the contact among active substances is further improved by high compaction.
3. The invention adopts two preparation methods simultaneously, can fully play the synergistic effect of lithium iron manganese phosphate and spinel lithium manganate, and preferably adopts the second method to better solve the problem of agglomeration of nano-inorganic solid electrolyte, better construct a lithium ion channel and improve the cycle performance.
Drawings
Fig. 1 is a graph of the conductivity of the positive electrode composite.
Fig. 2 is a graph comparing the cycle life of square aluminum cell prepared in example 1 and comparative example 1.
Fig. 3 is a graph comparing the cycle life of square aluminum cell prepared in example 3 and comparative example 2.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
Example 1
4kg of lithium manganate, 1kg of lithium manganese iron phosphate, 0.1kg of LATP, 0.06kg of sp, 0.09kg ofkg CNTs and 0.2kg PVDF were added to a 10L planetary mixer. Wherein the lithium manganate is a volumetric type lithium manganate D50The grain diameter is 15 mu m, and the lithium manganese iron phosphate is LiMn0.6Fe0.4PO4，D50The particle size was 1 μm. The stirrer revolves for 30r/min and is stirred for 0.5h, 1kg of NMP is added, then the rotation speed is opened for 1000r/min and the stirring is carried out for 1h, and the mixed materials are made into thick paste; then adding 1kg of NMP, raising revolution to 35r/min, opening a dispersion disc, gradually raising rotation speed to 3500r/min, stirring at high speed for 2h, and finally adding 0.3kg of NMP to adjust viscosity to obtain uniform anode slurry with the slurry viscosity of 12000 mpa.s.
Coating the slurry on an aluminum foil with the thickness of 15 mu m and drying, wherein the coating surface density is 230g/m2The pole piece is pressed by a roller press to ensure that the compacted density of the pole piece is 3.1g/cm3And obtaining the double-composite modified spinel lithium manganate positive plate.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 22.7Ah, and the 18.7Ah capacity is remained after the battery is cycled for 800 times at normal temperature.
Example 2
Adding 4kg of lithium manganate, 1kg of lithium manganese iron phosphate, 0.15kg of LLZO, 0.06kg of sp, 0.09kg of CNTs and 0.2kg of PVDF into a 10L planetary mixer, wherein the lithium manganate is single-crystal lithium manganate D50The grain diameter is 10 mu m, and the lithium manganese iron phosphate is LiMn0.8Fe0.2PO4，D50The particle size was 1.3. mu.m. The stirrer revolves for 30r/min and is stirred for 0.5h, 1kg of NMP is added, then the rotation speed is opened for 1000r/min and the stirring is carried out for 1h, and the mixed materials are made into thick paste; then adding 1kg of NMP, raising the revolution to 35r/min, opening a dispersion disc, gradually raising the rotation speed to 3500r/min at 1000r/min, stirring at high speed for 2h, and finally adding 0.8kg of NMP to adjust the viscosity to obtain uniform anode slurry with the slurry viscosity of 10500 mpa.s.
Coating the slurry on an aluminum foil with the thickness of 15 mu m and drying, wherein the coating surface density is 250g/m2The pole piece is pressed by a roller press to ensure that the compacted density of the pole piece is 3.2g/cm3And obtaining the double-composite modified spinel lithium manganate positive plate.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 22.5Ah, and the 18.5Ah capacity is remained after the battery is cycled for 800 times at normal temperature.
Example 3
4kg of lithium manganate, 1kg of lithium manganese phosphate, 0.06kg of sp, 0.09kg of CNTs and 0.2kg of PVDF were charged into a 10L planetary mixer. Wherein the lithium manganate is a volumetric type lithium manganate D50The grain diameter is 15 mu m, and the lithium manganese iron phosphate is LiMn0.6Fe0.4PO4，D50The particle size was 1 μm. The stirrer revolves for 30r/min and is stirred for 0.5h, 1kg of NMP is added, then the rotation speed is opened for 1000r/min and the stirring is carried out for 1h, and the mixed materials are made into thick paste; then adding 1kg of NMP, raising the revolution to 35r/min, opening a dispersion disc, gradually raising the rotation speed to 3500r/min at 1000r/min, stirring at high speed for 2h, and finally adding 0.3kg of NMP to adjust the viscosity to obtain uniform anode slurry A, wherein the slurry viscosity is 10100 mpa.s. Coating the slurry A on an aluminum foil with the thickness of 15 mu m and drying to obtain a substrate, wherein the coating surface density is 230g/m2。
0.1kg of LATP, 0.02kg of PVDF and 0.2kg of NMP are added into a sand mill, the diameter of a zirconia ball is 0.3mm, the mass ratio of the zirconia ball to a material is 10:1, the rotation speed of the sand mill is 2000r/min, the grinding time is 10min, slurry B is obtained, the viscosity is 6000mpa.s, and the slurry B is coated on a substrate, and the coating thickness is 2 mu m.
Tabletting by using a roller press to ensure that the compacted density of the pole piece is 3.1g/cm3And obtaining the double-composite modified spinel lithium manganate positive plate.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 22.3Ah, and the 18.8Ah capacity is remained after the battery is cycled for 800 times at normal temperature.
Example 4
Adding 4kg of lithium manganate, 1kg of lithium manganese phosphate, 0.06kg of sp, 0.09kg of CNTs and 0.2kg of PVDF into a 10L planetary mixer, wherein the lithium manganate is single-crystal lithium manganate D50The grain diameter is 10 mu m, and the lithium manganese iron phosphate is LiMn0.8Fe0.2PO4，D50The particle size was 1.3. mu.m. The stirrer revolves for 30r/min and is stirred for 0.Adding 1kg of NMP after 5h, then opening the rotation speed to 1000r/min, stirring for 1h again, and mixing the materials into a thick paste; then adding 1kg of NMP, raising the revolution to 35r/min, opening a dispersion disc, gradually raising the rotation speed to 3500r/min at 1000r/min, stirring at high speed for 2h, and finally adding 0.3kg of NMP to adjust the viscosity to obtain uniform anode slurry A, wherein the slurry viscosity is 9500 mpa.s. Coating the slurry A on an aluminum foil with the thickness of 15 mu m and drying to obtain a substrate, wherein the coating surface density is 250g/m2。
0.15kg of LLZO, 0.02kg of PVDF and 0.2kg of NMP are added into a sand mill, the diameter of a zirconia ball is 0.3mm, the mass ratio of the zirconia ball to the materials is 10:1, the rotating speed of the sand mill is 2000r/min, the grinding time is 10min, and slurry B with the viscosity of 7000mpa.s is obtained. Slurry B was coated onto a substrate to a thickness of 2 μm.
Tabletting by using a roller press to ensure that the compacted density of the pole piece is 3.2g/cm3And obtaining the double-composite modified spinel lithium manganate positive plate.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 22.1Ah, and the 18.5Ah capacity is remained after the battery is cycled for 800 times at normal temperature.
Comparative example 1
5kg of lithium manganate, 0.1kg of LATP, 0.06kg of sp, 0.09kg of CNTs and 0.2kg of PVDF were put into a 10L planetary mixer, wherein the lithium manganate was a volumetric type lithium manganate D50The particle size was 15 μm. The stirrer revolves for 30r/min and is stirred for 0.5h, 1kg of NMP is added, then the rotation speed is opened for 1000r/min and the stirring is carried out for 1h, and the mixed materials are made into thick paste; then adding 1kg of NMP, raising the revolution to 35r/min, opening a dispersion disc, gradually raising the rotation speed to 3500r/min at 1000r/min, stirring at high speed for 2h, and finally adding 0.3kg of NMP to adjust the viscosity to obtain uniform anode slurry with the slurry viscosity of 11500 mpa.s.
Coating the slurry on an aluminum foil with the thickness of 15 mu m and drying, wherein the coating surface density is 230g/m2The pole piece is pressed by a roller press to ensure that the compacted density of the pole piece is 3.0g/cm3And obtaining the positive plate for comparison.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 21.9Ah, and the battery has 15.9Ah capacity remained after 694 times of normal-temperature circulation.
Comparative example 2
5kg of lithium manganate, 0.06kg of sp, 0.09kg of CNTs and 0.2kg of PVDF were put into a 10L planetary mixer, wherein the lithium manganate was a volumetric type lithium manganate D50The particle size was 15 μm. The stirrer revolves for 30r/min and is stirred for 0.5h, 1kg of NMP is added, then the rotation speed is opened for 1000r/min and the stirring is carried out for 1h, and the mixed materials are made into thick paste; then adding 1kg of NMP, raising the revolution to 35r/min, opening a dispersion disc, gradually raising the rotation speed to 3500r/min at 1000r/min, stirring at high speed for 2h, and finally adding 0.3kg of NMP to adjust the viscosity to obtain uniform anode slurry A with the viscosity of 10800 mpa.s. Coating the slurry A on an aluminum foil with the thickness of 15 mu m and drying to obtain a substrate, wherein the coating surface density is 250g/m2。
Adding 0.1kg of LATP, 0.02kg of PVDF and 0.2kg of NMP into a sand mill, wherein the diameter of a zirconia ball is 0.3mm, the mass ratio of the zirconia ball to a material is 10:1, the rotating speed of the sand mill is 2000r/min, the grinding time is 10min, and uniform slurry B with the viscosity of 7000mpa.s is obtained; slurry B was coated onto a substrate to a thickness of 2 μm.
Tabletting by using a roller press to ensure that the compacted density of the pole piece is 3.1g/cm3And obtaining the positive plate for comparison.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 21.7Ah, and the battery has 15.8Ah capacity remained after being cycled for 800 times at normal temperature.
In conclusion, the capacity maintenance rates of the lithium ion batteries prepared in the examples exceed 82% after the lithium ion batteries are cycled for 800 times at normal temperature; and after the lithium ion battery prepared by the comparative example is cycled for 800 times at normal temperature, the capacity maintenance rate is lower than 73 percent. The result shows that the double-composite modified spinel lithium manganate positive plate can better construct a lithium ion channel and is beneficial to improving the cycle performance of a lithium ion battery.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The double-composite modified spinel lithium manganate positive plate is characterized by being prepared from 6-9 parts by mass of spinel lithium manganate, 1-4 parts by mass of lithium manganese iron phosphate, an inorganic solid electrolyte, a conductive agent and a binder; the mass of the inorganic solid electrolyte is 0.3-3% of the total mass of the spinel lithium manganate and the lithium iron manganese phosphate.
2. The double-composite modified spinel lithium manganate positive electrode sheet of claim 1, wherein said spinel lithium manganate is a capacity type lithium manganate, D509 to 18 μm; or the spinel lithium manganate is single crystal lithium manganate D506 to 12 μm.
3. The double-composite modified spinel lithium manganate positive plate of claim 1, wherein said lithium iron manganese phosphate is LiMn0.5Fe0.5PO4、LiMn0.6Fe0.4PO4、LiMn0.7Fe0.3PO4、LiMn0.8Fe0.2PO4、LiMn0.9Fe0.1PO4One kind of (1).
4. The double-composite modified spinel lithium manganate positive plate of claim 1, wherein D of said lithium iron manganese phosphate501-3 μm, and electron conductivity greater than 10-4S/cm。
5. The dual composite modified spinel lithium manganate positive plate of claim 1, wherein said inorganic solid electrolyte is one of lithium aluminum titanium phosphate, lithium lanthanum titanate, lithium lanthanum zirconium oxide, D50Is 50 to 300 nm.
6. The preparation method of the double-composite modified spinel lithium manganate positive electrode sheet according to any one of claims 1 to 5, characterized by comprising the step (i) or the step (ii):
(i) mixing spinel lithium manganate, lithium manganese phosphate, inorganic solid electrolyte, conductive agent and binder by a dry method, adding N-methyl pyrrolidone, and mixing to form a viscous paste; adding N-methyl pyrrolidone, and stirring at a high rotating speed to obtain a slurry with the viscosity of 10000-30000 mpa.s; coating the slurry on a current collector, drying, and rolling to obtain the double-composite modified spinel lithium manganate positive plate;
(ii) mixing spinel lithium manganate, lithium manganese phosphate, a conductive agent and part of a binder by a dry method, adding N-methyl pyrrolidone, and mixing to form a viscous paste; adding N-methyl pyrrolidone, increasing the rotating speed, stirring, and adjusting the viscosity of the slurry to 10000-30000 mpa.s to obtain slurry A; carrying out sanding nanocrystallization on the inorganic solid electrolyte, the residual binder and N-methyl pyrrolidone to prepare slurry B with the viscosity of 5000-10000 mpa.s; coating the slurry A on a current collector and drying, coating the slurry B on the current collector and drying, and rolling to obtain the double-composite modified spinel lithium manganate positive plate.
7. The preparation method of the double-composite modified spinel lithium manganate positive electrode sheet according to claim 6, wherein in steps (i) and (ii), the solid content of the slurry is 40% -70%.
8. The preparation method of the double-composite modified spinel lithium manganate positive electrode sheet according to claim 6, characterized in that in step (i), the coating density of the slurry is 150-300 g/m2(ii) a In the step (ii), the coating density of the slurry A is 150-300 g/m2The coating thickness of the slurry B is 1-3 mu m.
9. Preparation of double-composite modified spinel lithium manganate positive electrode sheet according to claim 6The method is characterized in that in the steps (i) and (ii), the compacted density after rolling is 3.1-3.4 g/cm3。
10. A lithium ion battery, which comprises a positive plate, a negative plate, electrolyte and a diaphragm, and is characterized in that the positive plate is the double-composite modified spinel lithium manganate positive plate of any one of claims 1 to 5.
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